Spray application systems components comprising a repellent surface comprising a siloxane material &amp; methods

ABSTRACT

Presently described are components of a spray application system. At least one component comprises a liquid repellent surface layer. The liquid repellent surface (e.g. layer) comprises a siloxane material. The component is typically a liquid reservoir, a liquid reservoir liner, a lid for a liquid reservoir or liner, or a combination thereof. In some embodiments, the component comprises a thermoplastic polymeric material. In some favored embodiments, the component is a removable liquid reservoir or liner. In some favored embodiments, the component is a collapsible liquid reservoir or liner. The spray application system typically further comprises a gravity-fed spray gun. Also described are spray application systems, methods of using a spray application system, as well as methods of making a component of a spray application system wherein the component has a liquid repellent surface.

BACKGROUND

As described for example in WO98/32539, spray application systems forspraying liquids (e.g. paints, garden chemicals etc.) are generallyknown. Such systems generally comprise a reservoir to contain a liquidand a spray gun through which the liquid is dispensed. The liquid may befed from the reservoir under gravity and/or it may be entrained in astream of pressurized liquid, for example air or water, which issupplied to the gun from an external source.

As also described in WO98/32539 disposable liners have been used with(e.g. re-usable) liquid reservoirs. The liner may aid in disposal of thecontents; protect the reservoir or its contents; as well as facilitateor even eliminate the cleaning of the reservoir.

SUMMARY

With current spray (e.g. paint) application systems, a portion of theliquid (e.g. paint) is retained within the liquid reservoir or linerafter dispensing the liquid. Depending on the size of the liquidreservoir or liner, the amount of retained paint may range from about ½to 1 ounce. In the case of relatively expensive liquids, such as coloredautomobile base coat paints that can cost $3-$6 per sprayable ounce, thecost of such wasted retained (e.g. paint) liquid can be substantial.Thus, industry would find advantage in minimizing the amount of paint orother liquid that is retained on components of spray applicationsystems.

One commonly known class of fluoropolymer is Teflon™ PTFE resin or inother words polytetrafluoroethylene polymers prepared by thepolymerization of the monomer tetrafluoroethylene (“TFE” having thestructure CF₂═CF₂). Teflon™ PTFE resins are described as crystallinematerials. Crystalline PTFE resins typically have a density of about 2.2g/cm³.

It has been found that Teflon™ PTFE does not provide a liquid repellentsurface such that the receding contact angle with water is at least 90degrees and/or the difference between the advancing contact angle andthe receding contact angle of the surface with water is less than 10.Further, Teflon™ PTFE also does not provide an (e.g. aqueous) paintrepellent surface as determined by test methods set forth in theexamples.

Presently described are components of a spray application system. Atleast one component comprises a liquid repellent surface (e.g. layer).In some embodiments, the liquid repellent surface comprises a silane orsiloxane (e.g. polydimethylsiloxane) material, wherein the liquidrepellent surface is not a lubricant impregnated surface. In someembodiments, the liquid repellent surface comprises a (e.g. layer of)thermally processible polymer and a siloxane melt additive. Thecomponent is typically a liquid reservoir, a liquid reservoir liner, alid for a liquid reservoir or liner, or a combination thereof. In someembodiments, the component comprises a thermoplastic polymeric material.In some favored embodiments, the component is a removable liquidreservoir or liner. In some favored embodiments, the component is acollapsible liquid reservoir or liner. The spray application systemtypically further comprises a gravity-fed spray gun.

Also described are spray application systems, methods of using a sprayapplication system, as well as methods of making a component of a sprayapplication system wherein the component has a liquid repellent surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a spray application system;

FIG. 2 shows an exploded view of components of a liquid (e.g. paint)reservoir further comprising a liner for the gun of FIG. 1;

FIG. 3 shows the liquid reservoir of FIG. 2 in an assembled condition,with an adapter 21 for connecting the liquid reservoir to a spray gun;

FIG. 4 shows a longitudinal cross-section through the liquid reservoirand the adapter of FIG. 3;

FIG. 5 shows the collapsed liner after the liquid (e.g. paint) has beendispensed from a reservoir or liner;

FIG. 6 is cross-sectional view of another embodiment of an articlecomprising a liquid repellent surface;

FIG. 7 is cross-sectional view of another embodiment of an articlecomprising a liquid repellent surface;

FIG. 8 is cross-sectional view of another embodiment of an articlecomprising a liquid repellent surface; and

FIG. 9 is cross-sectional view of another embodiment of an articlecomprising a liquid repellent surface. The cross-sectional drawings arenot to scale.

DETAILED DESCRIPTION

FIG. 1 illustrates an embodied spray application system. The gun 1comprises a body 2, a handle 3 which extends downwards from the rear endof the body, and a spray nozzle 4 at the front end of the body. The gunis manually-operated by a trigger 5 which is pivotally-mounted on thesides of the gun. The liquid (e.g. paint) reservoir 6 is located on thetop of the body 2 and communicates with an internal (e.g. air)passageway (not visible) which extends through the gun from a connector7 at the lower end of the handle 3 to the nozzle 4. During use, liquid(e.g. paint) is provided in reservoir 6. Removable lid 8 is engaged withthe open end of (e.g. paint) liquid reservoir 6. Further, connector 7 isconnected to a source of compressed air (not shown) so that, when theuser pulls on the trigger 5, compressed air is delivered through the gunto the nozzle 4 (or functionally similar assembly) and entrains andatomizes paint being delivered under gravity from liquid reservoir 6.The liquid (e.g. paint) is then discharged through the nozzle 4 with thecompressed air, as a spray.

Various spray gun designs can be utilized in the embodied sprayapplication system, such as described for example in U.S. Pat. Nos.5,582,350; 5,267,693; and EP 0768 921. In some embodiments, the sprayapplication system may further comprise tubes or hoses, typicallydisposed between the (e.g. paint) liquid reservoir and the gun.

FIG. 2 illustrates the components of another embodied liquid (e.g.paint) reservoir 11 that can be used with the gun 1 of FIG. 1 (or anysimilar gun) instead of liquid (e.g. paint) reservoir 6. The liquid(e.g. paint) reservoir 11 comprises an open container 12, of suitablesize for attachment to a (e.g. hand-held) spray gun, having an air hole12A in its base and provided with a liner 13. The liner 13 correspondsin shape to and fits within the interior of container 12. The (e.g.removable) liner may have a narrow rim 14 at the open end that contactsthe top edge of the container 12. The container 12 also has a (e.g.disposable) lid 15. Lid 15 typically engages rim 14 of the open end ofthe liner 13 and is held firmly in place when lid 15 is attached tocontainer 12. The lid can be attached by an annular collar 20 whichscrews onto the container, such as depicted in FIG. 3.

Liquid reservoir 6 or container 12 of the liquid (e.g. paint) reservoir11 is typically formed from a self-supporting (e.g. rigid) thermoplasticpolymeric material, for example polyethylene or polypropylene, of anysuitable size. For use with paint spray guns, containers having acapacity ranging from 100 ml to 1 liter, such as a capacity of 250, 500or 800 ml, are common. The lid 15 is also typically formed from athermoplastic polymeric material, for example, polyethylene orpolypropylene. The lid may be transparent, translucent or opaque and mayoptionally be colored. The collar 20 may be a molded thermoplastic or itmay be a machined metal (for example, aluminum). In some embodiments,fluid reservoir 6 and container 12 are formed by injection molding of athermoplastic polymer.

Liquid reservoir 6, as well as liner 13, are typically alsoself-supporting but can also be collapsible, i.e. collapses when (e.g.paint) liquid is withdrawn from the liner or liquid (e.g. paint)reservoir during operation of the spray gun. In one embodiment, theliner 13 or liquid (e.g. paint) reservoir 6 have a (e.g. thicker) rigidbase 13A and (e.g. thinner) flexible side walls 13B. In this embodiment,the base may have a thickness of about 250 to 400 microns. In contrast,the side walls can range from about 100 to 250 microns and in someembodiments are no greater than 225, 200 or 175 microns. When the linercollapses, it typically collapses in the longitudinal (or axial)direction by virtue of the side walls collapsing rather than the base.Liner 13 and some embodiments of liquid (e.g. paint) reservoir 6 arepreferably formed by thermo/vacuum forming a sheet of thermoplasticmaterial such as low density polyethylene (LDPE). When the liner 13 orliquid (e.g. paint) reservoir 6 is collapsible it can be characterizedas a single-use or in other words “disposable” component.

The lid 15 typically includes a (e.g. central) aperture 16 from whichextends a connector tube 17 provided, at its end, with outwardextensions 18 forming one part of a connection, such as a bayonetconnection; i.e. a fitting engaged by being pushed into a socket andthen twisted to lock in place. The liquid (e.g. paint) reservoir 11 canbe attached to the spray gun 1 through the use of an adapter 21 asdepicted in FIG. 3 and FIG. 4. The adapter 21 is a tubular componentwhich, at one end 22, is formed internally with the other part of the(e.g. bayonet) connection for attachment to the connector tube 17. Theother end 23 of the adapter can be shaped to match the standardattachment of the spray gun (typically a screw thread). The adapter 21may be a machined metal component and may, for example, be formed fromanodized aluminum or stainless steel.

During use of the spray application system, adapter 21 is securelyattached (at end 23) to the spray gun. Liner 13 is inserted intocontainer 12. Liquid (e.g. paint) is then put into liner 13, lid 15 ispushed into place, and collar 20 engaged (e.g. screwed down) tightlywith container 12 to hold the lid in position. The rim 14 of the liner13 is typically held in place between lid 15 and container 12 as shownin FIG. 4. As paint is removed from within the liner 13, the sides ofthe liner collapse as depicted in FIG. 5 as a result of the decreasedpressure within the liner. The base of the liner, being more rigid,retains its shape so that the liner tends to collapse in thelongitudinal rather than the transverse direction thereby reducing thepossibility of pockets of paint being trapped in the liner.

The liner 13 typically has a smooth (e.g. continuous) internal surface,lacking structures that would increase retention of the liquid (e.g.paint). Thus, the liner typically has no discontinuities (projections orindentations) from a planar surface such as pleats, corrugations, seams,joints, gussets, or groove(s) at the internal junction of the side walls13B with the base 13A. Further, the liner volumetrically coincides withthe inside of the container 12.

Liquid (e.g. paint) can be mixed within liner 13 or within liquid (e.g.paint) reservoir 6. To facilitate the use as a mixing receptacle, theside walls of the container 12 or liquid (e.g. paint) reservoir 6 may beprovided with markings 25 (FIGS. 2 and 3) enabling the volume of thecontents within the container to be determined.

Although fluid reservoir 6, container 12, and liner 13 may be opaque,such components are preferably transparent or translucent such that theliquid can be visually observed through the walls. This can alsofacilitate using the fluid reservoir 6, or container 12 and liner 13 asa measuring and mixing receptacle.

Liquid (e.g. paint) contained in the liquid reservoir 6 or liner 13 isoften mixed by hand. Hand mixing can be beneficial to avoid airentrapment. The inside surfaces of the liquid reservoir 6 or liner 13are also typically not exposed to high amounts of mixing forces whenmixed by hand. However, the side walls of the mixing container may be‘scraped’ in order to ensure all of the toners and other ingredients arethoroughly mixed.

In some embodiments, the liners are thermoformed, injection molded, blowmolded (or formed using some other plastic processing technique) frommaterials such as, but not necessarily limited to, low densitypolyethylene, polypropylene, polyethylene, and/or blends thereof.Suitable liner components are commercially available from 3M Company,St. Paul, Minn. under trade designation “3M PPS PAINT PREPARATIONSYSTEM”.

To ensure that there are no unwanted particles, the liquid (e.g. paint)typically passes through a (e.g. removable) filter as the (e.g. paint)liquid passes from the liquid reservoir 6 or liner 13 to the spray gunor nozzle during use of the spray application system. Such filter can bepositioned at various locations. In one embodiment, aperture 16 iscovered by a filter mesh 19 which may be a push fit into the aperture ormay be an integral part of the lid 15, as depicted in FIG. 4. In anotherembodiment, a filter may be provided within liquid reservoir 6, asdescribed and depicted in FIG. 12 of WO 98/32539.

FIGS. 1-9 depict examples of illustrative liquid (e.g. paint)reservoirs, liquid reservoir liners, lids for liquid (e.g. paint)reservoirs and liners. Such components may optionally include variousother adaptations as known in the art for spray application systems, asdescribed for examples in WO 98/32539.

In the present invention, a component (e.g. a liquid reservoir, a liquidreservoir liner, a lid for a liquid reservoir or liner, or a combinationthereof) of a spray application system comprises a liquid repellentsurface (e.g. layer). The liquid repellent surface layer may be presenton a portion of a surface of at least one of such components or theliquid repellent surface layer may be present on the entire surface thatcomes in contact with liquid (e.g. paint) during use. Although theexterior surfaces of the liquid reservoir, liner, lid, etc. may comprisethe liquid repellent surface layer described herein, in typicalembodiments, the interior surface(s) of at least one of such componentscomprises a liquid repellent surface layer.

When the liquid (e.g. paint) repellent surface comprises a lubricantimpregnated into pores of a porous layer as described in WO2016/069674,the outer exposed surface is predominantly liquid lubricant. Somestructures of the porous layer may protrude through the liquid lubricantand be present at the outer exposed surface. However, the outer exposedsurface is predominantly liquid lubricant. In this embodiment, typicallyat least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% or greater of thesurface area is a liquid lubricant, as can be determined by microscopy.Thus, the aqueous liquid (e.g. paint) that is being repelled comes incontact with and is repelled by the liquid lubricant.

By “liquid” it is meant that the lubricant has a dynamic (shear)viscosity of at least about 0.1, 0.5, or 1 mPa-s and no greater than 10′mPa-s at the use temperature. In typical embodiments, the dynamicviscosity is no greater than 10⁶, 10⁵, 10⁴, or 10³ mPa-s. The dynamicviscosity values described herein refer to those measured at a shearrate of 1 sec⁻¹.

In other embodiments as described herein, the liquid (e.g. paint)repellent surface of the spray application system component is not alubricant impregnated surface. Rather the outer exposed surface ispredominantly a solid liquid (e.g. paint) repellent material. In thisembodiment, less than 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1,0.5, 0.1, 0.005, or 0.001% of the surface area is a liquid lubricant.Rather, at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99,or 99.5% or greater of the outer exposed surface is a solidliquid-repellent material. Thus, the aqueous liquid (e.g. paint) that isbeing repelled comes in contact with and is repelled by the solidliquid-repellent material.

The solid liquid (e.g. paint) repellent material is generally a solid atthe use temperature of the spray application system component, whichcommonly ranges from 40° F. to 120° F. In typical embodiments, the solidliquid (e.g. paint) repellent material is a solid at room temperature(e.g. 25° C.). Thus, the solid liquid (e.g. paint) repellent materialhas a melting temperature (peak endotherm as measured by DifferentialScanning calorimetry) greater than 25° C., and typically greater than120° F. (49° C.). In some embodiments, the solid liquid (e.g. paint)repellent material has a melting temperature no greater than 200° C. Thesolid (e.g. paint) repellent material may exhibit more than one meltingtemperature. In typical embodiments, a single solid liquid (e.g. paint)repellent material is utilized. However, when the liquid repellentsurface is provided by a coating composition, the coating compositionmay contain a mixture of solid liquid (e.g. paint) repellent materials.

With reference to FIG. 6, article 200 is a component of a sprayapplication system comprising substrate or component 210 (e.g. a liner,liquid reservoir, or lid) comprising a liquid (e.g. paint) repellentsurface 253 that comprises a (e.g. non-fluorinated) organic polymericbinder and a siloxane (e.g. polydimethylsiloxane “PDMS”) material. Theconcentration of siloxane (e.g. PDMS) material at the outer exposedsurface (e.g. layer) 253 is typically higher than the concentrationwithin the (e.g. non-fluorinated) organic polymeric binder layer 251proximate substrate 210. In one embodiment, the liquid (e.g. paint)repellent surface (e.g. layer) can be provided by coating substrate 210with a coating composition comprising an organic solvent, a (e.g.non-fluorinated) organic polymeric binder, and a siloxane (e.g. PDMS)material as will subsequently be described.

With reference to FIG. 7, article 300 is a component of a sprayapplication system comprising substrate or component 310 (e.g. a liner,liquid reservoir, or lid) comprising a liquid (e.g. paint) repellentsurface (e.g. layer) 353 that comprises a siloxane (e.g. PDMS) material.The concentration of siloxane (e.g. PDMS) material at the outer exposedsurface (e.g. layer) 353 is typically higher than the concentration ofsiloxane (e.g. PDMS) material proximate the center of the substrate 310.In one embodiment, the liquid (e.g. paint) repellent surface 353 can beprovided by including a siloxane (e.g. PDMS) material as a melt additivein a polymeric material that is thermally processed to form substrate310 into a component such as a liner, liquid reservoir, or lid.

With reference to FIG. 8, article 400 is a component of a sprayapplication system comprising substrate or component 410 (e.g. a liner,liquid reservoir, or lid) comprising a liquid (e.g. paint) repellentsurface 453 that comprises a siloxane (e.g. PDMS) polymer layer, or apolymer comprising both fluorinated and silane or siloxane groups 451.In one embodiment, the liquid (e.g. paint) repellent surface 453 can beprovided by coating substrate 410 with a coating composition comprisingan organic solvent and a siloxane (e.g. PDMS) polymer, as willsubsequently be described. The siloxane content is typically the samethroughout the thickness of the siloxane layer. In another embodiment,the liquid (e.g. paint) repellent surface 453 can be provided bycoextruding substrate 410 together with a siloxane (e.g. PDMS) polymerlayer 451 into a sheet and thermally processing the sheet into a liner,liquid reservoir, or lid.

With reference to FIG. 9, article 500 is a substrate or component 510 ofa spray application system such as a liner, liquid reservoir, or lid,comprising a siloxane (e.g. PDMS) polymer. The siloxane content istypically the same throughout the thickness of the component. Theinterior and exterior surface of the component typically comprisesiloxane polymer. In another embodiment, the liquid (e.g. paint)repellent surface can be provided by thermally processing a siloxanepolymer or a polymer comprising both fluorinated and silane or siloxanegroups into a component such as a liner, liquid reservoir, or lid.

In other embodiments, the (e.g. paint) liquid repellent surfacecomprises a siloxane (e.g. PDMS) material and a (e.g. non-fluorinated)organic polymeric binder. In typical embodiments, a major amount ofnon-fluorinated polymeric binder is combined with a sufficient amount ofsiloxane (e.g. PDMS) material that provides the desired repellencyproperties, as described herein.

In typical embodiments, the amount of siloxane (e.g. PDMS) material isat least about 0.05, 0.1, 0.25, 0.5, 1.5, 2.0 or 2.5 wt.-% and in someembodiments, at least about 3.0, 3.5, 4.0, 4.5 or 5 wt.-%. The amount ofsiloxane (e.g. PDMS) material is typically no greater than 50, 45, 40,35, 30, 25, 20, 15, or 10 wt.-% of the sum of the siloxane (e.g. PDMS)material and non-fluorinated polymeric binder.

In other embodiments, the (e.g. paint) liquid repellent surfacecomprises a siloxane (e.g. PDMS) material. In some embodiments, thesiloxane (e.g. PDMS) material is a solid rather than a liquid (e.g.lubricant) at 25° C. and at temperatures ranging from 40° F. (4.44° C.)to 130° F. (54.4° C.). In typical embodiments the siloxane (e.g. PDMS)material is free of fluorinated groups and thus free of fluorine atoms.However, in other embodiments, a predominantly siloxane (e.g. PDMS)material may further comprise one or more fluorinated groups. Althoughit is most common to utilize a siloxane (e.g. PDMS) material,combinations of a fluorochemical material and a siloxane (e.g. PDMS)material can be utilized.

In some embodiments, a major amount of non-fluorinated polymeric binderor thermally processible polymer is combined with a sufficient amount ofsiloxane (e.g. PDMS) material that provides the desired repellencyproperties, as described herein.

In some embodiments, the silicone material is a compound, oligomer orpolymer having a polysiloxane backbone and more typically apolydimethylsiloxane backbone. The polysiloxane backbone may furthercomprise pendent groups, such as hydrocarbon (e.g. preferably alkyl)groups. Such pendent groups contain more than one carbon atoms. Thesilicone material typically does not comprise vinyl groups or otherpolymerizable groups that would result in the silicone material forminga crosslinked network.

In some embodiments, the siloxane (e.g. PDMS) material (e.g. oligomer orpolymer) comprises at least 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95wt.-% polydimethylsiloxane backbone. The siloxane (e.g. PDMS) materialmay further comprise pendent longer chain hydrocarbon (e.g. preferablyalkyl) groups in an amount of at least 5, 10, 15, 20, 25, 30, or 35wt.-% of the siloxane (e.g. PDMS) material.

The siloxane (e.g. PDMS) oligomer may have a molecular weight (Mn) of atleast 1500 or 2000 g/mole as measured by GPC. The siloxane oligomertypically has a molecular weight (Mn) no greater than 10,000, 9000,8000, or 7000 g/mole. The siloxane (e.g. PDMS) polymer typically has amolecular weight (Mn) greater than 10,000; 15,000; or 20,000 g/mole. Insome embodiments, the molecular weight of the siloxane polymer is nogreater than 100,000; 75,000; or 50,000 g/mole.

In some embodiments, the siloxane (e.g. PDMS) material comprises pendentlonger chain hydrocarbon (e.g. preferably alkyl) groups wherein thelonger chain hydrocarbon (e.g. preferably alkyl) groups average at least8, 10, 12, 14, 16, 18, or 20 carbon atoms. In some embodiments, thesiloxane (e.g. PDMS) material comprises pendent longer chain hydrocarbon(e.g. preferably alkyl) groups wherein the longer chain hydrocarbon(e.g. preferably alkyl) groups average greater than 20 carbons atomssuch as at least 25, 30, 35, or 40. The pendent longer chain hydrocarbon(e.g. preferably alkyl) groups typically average no greater than 75, 70,65, 60, or 50 carbon atoms.

In some embodiments, the siloxane (e.g. PDMS) material may becharacterized as an alkyl dimethicone. The alkyl dimethicone comprisesat least one linear, branched, or cyclic alkyl group averaging at least8, 10, or 12 carbon atoms such as lauryl dimethicone, depicted asfollows:

In some embodiments, the alkyl dimethicone comprises at least onelinear, branched, or cyclic alkyl group averaging at least 14, 16, or 18carbon atoms such as cetyl dimethicone and stearyl dimethicone.

These materials are characterized by having a (e.g. linear) polysiloxanebackbone having terminal alkyl (C1-C4, typically methyl) silane groupsand a pendent (e.g. linear) alkyl group.

Preferred alkyl dimethicones typically have the structure:

wherein the sum of (a+b+c) is between about 100 and 1000, for examplebetween about 200 and 500 or between about 300 and 400; the ratio of ato the sum of (b+c) is about 99.9:0.1 to 80:20, or about 99:1 to 85:15,or about 99:1 to 90:10, or about 99:1 to 92:8, or about 98:2 to 93:7 orabout or about 98:2 to 94:6; R¹ is a linear, branched, or cyclic alkylgroup having between 20 and 50 carbon atoms, for example about 22 to 46carbon atoms, or about 24 to 40 carbon atoms; R² is a linear, branched,or cyclic alkyl or alkaryl group having between 2 and 16 carbons, forexample about 4 to 16, or about 5 to 12, or about 6, to 10, or about 8carbon atoms; and the structure is a random, block, or blocky structure.In some embodiments, the ratio of a to (b+c) in conjunction with thenumber of carbons in the R¹ and R² groups result in an alkyldimethicones having greater than about 50 wt. % dimethyl siloxane (a)units, or in embodiments greater than about 60 wt. % dimethyl siloxaneunits. In some embodiments, c is 0. In some embodiments, the sum of(a+b+c) is about 300 to 400 and the ratio of “a” to the sum of (b+c) isabout 98:2 to 94:6. In some embodiments, the alkyl dimethicone is ablend of two or more species thereof, wherein the species differ interms of the sum of (a+b+c), the ratio of “a” to the sum of (b+c), thevalue of c, or in two or more such parameters. In some embodiments, thealkyl dimethicone is a random structure. In some embodiments, R¹ is alinear alkyl group. In some embodiments, R² is a linear alkyl group.

The alkyl dimethicone materials of the Formula I above are characterizedby having a (e.g. linear) polysiloxane backbone having terminal alkyl(C1-C4, typically methyl) silane groups and a plurality of pendent (e.g.linear) alkyl groups.

Methods of synthesizing alkyl dimethicones are known in the art. See forexample U.S. Pat. No. 9,187,678; incorporated (entirely) herein byreference.

While the structures of alkyl dimethicones are generally preferablylinear structures, it will be understood by those of skill that suchstructures as synthesized or purchased can include an (e.g. small)amount of branching. Such branching, using terminology understood bythose of skill, is referred to as “T” and “Q” functionality. In any ofthe embodiments herein, a substantially linear alkyl dimethiconestructure can contain an amount of T branching, Q branching, or both.

In some embodiments, the siloxane (e.g. alkyl dimethicone) material hasa melting temperature (e.g. peak endotherm as measured by DSC) of atleast 140° F. (60° C.) or 150° F. (65.6° C.) ranging up to 170° F.(76.7° C.), 175° F. (79.4° C.), or 180° F. (82.2° C.).

In some embodiments, the siloxane (e.g. PDMS) material may becharacterized as a high molecular weight or ultra high molecular weight(UHMW) polydimethylsiloxane (e.g. melt additive) material. In someembodiments, the siloxane (e.g. PDMS) material has a viscosity of atleast 10,000 centistokes; 25,000 centistokes; or 50,000 centistokesranging up to 100,000 centistokes. In other embodiments, the siloxane(e.g. PDMS) material has a viscosity at 25° C. greater than 100,000centistokes. The viscosity may be at least 250,000 mPa centistokes;500,000 mPa centistokes; 1,000,000 mPa centistokes; or 5,000,000centistokes; and typically less than 10,000,000 centistokes mPa. In yetother embodiments, the siloxane (e.g. PDMS) material may becharacterized as an ultra high molecular weight (UHMW) siloxane (e.g.PDMS) material having a viscosity greater than 10 million centistokesranging up to 50 million centistokes.

The high and ultra high molecular weight siloxane (e.g. PDMS) materialtypically comprises little or no material having a viscosity less than10,000 centistokes, or less than 5,000 centistokes, or less than 2500centistokes, or less than 1000 centistokes. The ultra high molecularweight (UHMW) siloxane (e.g. PDMS) material typically comprises littleor no material having a viscosity within the 10,000 centistokes to100,000 centistokes. Further, the ultra high molecular weight (UHMW)siloxane (e.g. PDMS) material typically comprises little or no materialhaving a viscosity within the 100,000 centistokes to 1,000,000 mPacentistokes. When the siloxane material comprises little or no siloxane(e.g. PDMS) material of certain viscosities, the amount is less than 5,4, 3, 2, 1, 0.5 or 0.1 wt.-% based on the total weight of the siloxane(e.g. PDMS) material. Unless specified otherwise, the viscosity valuesdescribed herein refer to those measured at a temperature of 25° C. anda shear rate of 1 sec⁻¹.

Siloxane material melt additives often comprise a polydimethylsiloxanebackbone. Some of the methyl groups can be substituted with functionalgroups to adjust the compatibility and mobility within the thermallyprocessible polymer. Addition-reaction silicone elastomers, such aspoly-vinyl siloxane (i.e. vinyl polysiloxane) are a viscous liquid thatcure (i.e. chemically crosslink vinyl or other reactive groups) into arubber-like solid, taking the shape or profile of the surface it is incontact with while curing. Such materials may be characterized asthermosets. Unlike addition-reaction silicone elastomers, in someembodiments the siloxane (e.g. PDMS) material melt additives are notchemically crosslinked and generally do not contain appreciable amountsof ethylenically unsaturated groups, such as vinyl groups or otherreactive groups. In other embodiments, some of the PDMS may comprisedimethylvinyl terminal groups. Further, some of the PDMS may be hydroxylterminated. The concentration of such ethylenically unsaturated groups(e.g. vinyl) or other reactive groups is typically sufficiently low suchthat the siloxane material is a thermoplastic material and/or suitablefor thermally processing after chemical crosslinking of such groups.

In some embodiments, the siloxane (e.g. PDMS) material melt additivesare commercially available preblended with a thermally processiblepolymer as a “masterbatch”. For example, ultra high molecular weight(UHMW) polydimethylsiloxane, having a siloxane content of 50% isavailable predispered in low density polyethylene (LDPE), melt flowindex 8, from Dow Corning™ under the trade designation “MB50-002Masterbatch”. In some embodiments the LDPE may also contain silica (e.g.talc). Although the masterbatch is a solid material typically in theform of pellets or a powder, according to literature the siloxane (e.g.PDMS) material contained therein flows like a molten polymer, yet canhave a higher molecular weight than silicone oils typically utilized aslubricants of a lubricant impregnated surface.

The component (e.g. liner) of the spray application system is preferablyprepared in a manner such that the siloxane (e.g. PDMS) material meltadditive sufficiently separates from the thermally processible polymerit is admixed with and migrates to the surface of the component. Whenthe separation or migration of siloxane (e.g. PDMS) material meltadditive is insufficient, a liquid (e.g. paint) repellent surface, asdescribed herein, is not obtained. An insufficient concentration ofsiloxane (e.g. PDMS) material melt additive can also result in notobtaining a liquid (e.g. paint) repellent surface. In some embodiments,the component or liquid (e.g. paint) repellent surface may be subjectedto a heat treatment to facilitate the separation of the siloxane (e.g.PDMS) material melt additive from the bulk of the thermally processiblepolymer. Such heat treatment may occur for example, when a liner isthermoformed from a sheet prepared by extrusion, the liner may havebetter liquid (e.g. paint) repellency than the sheet from which it wasprepared.

In some embodiments, the siloxane material may be characterized as asiloxane copolymer or silicone-containing copolymer. The above describedalkyl dimethicone is one class of siloxane copolymer. However, otherclasses of siloxane copolymers are also suitable.

Siloxane copolymers are generally prepared using methods such as livinganionic polymerization, ring-opening polymerization (ROP), atom transferradical polymerization (ATRP), and step-growth polymerization. Siloxanecopolymers may be characterized for example as grafted, segmented, orblock copolymers. The block copolymers, can have various structures,most commonly a diblock or triblock structure.

Although the most common siloxane polymer backbone ispolydimethylsiloxane (PDMS), the backbone of the siloxane polymer mayinclude other substituents or polymerized units derived from othermonomers, especially non-reactive polymerized units such a methyl phenylsiloxane, diphenyl siloxane, or 3,3,3-trifluoropropylmethyl siloxane,and combinations thereof.

The polydiorganosiloxane (“polysiloxane”) backbone comprises repeatingunit of the formula:

wherein each R is independently a C₁₋₁₃ monovalent organic group. Forexample, R can be a C₁-C₁₃ alkyl, C₁-C₁₃ alkoxy, C₂-C₁₃ alkenyl group,C₂-C₁₃ alkenyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy, C₆-C₁₄ aryl,C₆-C₁₀ aryloxy, C₇-C₁₃ arylalkyl, C₇-C₁₃ aralkoxy, C₇-C₁₃ alkylaryl, orC₇-C₁₃ alkylaryloxy. In an embodiment, where a transparentpolysiloxane-polycarbonate is desired, R is preferably unsubstituted byhalogen. Combinations of the foregoing R groups can be used in the samecopolymer.

The value of E in the above formula can vary. Generally, E has anaverage value of at least 2, 5, or 10 and in some embodiments at least15, 20, 25, 30, 35, or 40. In typical embodiments E has an average valueup to 1,000. In some embodiments, E is no greater than 900, 800, 700,600 500, 400, 300, 200, or 100. In some embodiments, E is no greaterthan 90, 80, 70, or 60.

In some embodiments, the siloxane copolymer comprises 50, 55, 60, 65,70, 75, 80, 85, 90 or 95 wt.-% of polyorganosiloxane (e.g. PDMS)material, such as in the case of the previously described alkyldimethicone. In other embodiments, the siloxane copolymer comprises lessthan 50 wt.-% polyorganosiloxane (e.g. PDMS) material. In someembodiments, the siloxane copolymer comprises at least 1, 1.5, 2, 2.5,3, 3.5, 4, 4.5 or 5 wt.-% of polyorganosiloxane (e.g. PDMS) material. Inother embodiments, the siloxane copolymer comprises at least 10, 15, 20,25, or 30 wt.-% of polyorganosiloxane (e.g. PDMS) material.

Although in the case of the alkyl dimethicone copolymer depicted above,the alkyl group is bonded directly to a silicone atom of a siloxanebackbone, when the siloxane copolymer is prepared from other syntheticroutes the silicone copolymer may further comprise other groups withinthe copolymer. In such embodiments, the silicone copolymer may becharacterized as a silicone urea copolymer, silicone-urethane copolymer,silicone-ester copolymer, silicone amide copolymer, silicone imidecopolymer, etc.

The comonomer of the siloxane copolymer can be selected based on thecomposition of the component of the spray application system and/orbased on the intended method of making the component or repellentsurface thereof.

For example when the component of the spray application system is athermally processible material such as a polyolefin (e.g., LDPE) and therepellent surface is prepared by use of a siloxane material meltadditive, the siloxane copolymer melt additive may be an alkyldimethicone copolymer or a copolymer of polyolefin andpolyorganosiloxane (e.g. PDMS). Other siloxane copolymers that includepolyolefin are various block copolymers such as described in U.S. Pat.Nos. 5,618,903; 5,641,835 and 5,728,469; incorporated herein byreference. As yet another example, when the component of the sprayapplication system comprises polycarbonate, the siloxane copolymer meltadditive may be a polycarbonate siloxane copolymer.

Depending on the selection of the comonomer, the siloxane (e.g.copolymer) material may have a higher melting point or higher softeningpoint than the alkyl dimethicone copolymer depicted above. For example,in some embodiments, the Vicat Softening Temperature (ASTM D 1525, RateA/50) of the (e.g. polycarbonate) siloxane copolymer is at least 150° F.(65.6° C.), 200° F. (93.3° C.) or 250° F. (121.1° C.) ranging up to 275°F. (135° C.) or 300° F. (148.9° C.). Highly crosslinked (e.g. thermoset)siloxane materials generally do have a softening temperature in theranges just described.

In one embodiment, the polycarbonate siloxane copolymer comprisesstructural units of the formula:

where x and y are integers representing the number of repeating units;and x is at least one.

Such structural units may be characterized as the A block of a blockcopolymer.

The polycarbonate siloxane copolymer further comprises polycarbonatestructural units. In typical embodiments, the polycarbonate structuralunit has the formula:

Such structural units may be characterized as the B block of a blockcopolymer. Other aromatic polycarbonate structural units are depicted asfollows:

In one embodiment, the siloxane copolymer comprises structural units ofthe formula:

wherein x, y, and z of the polycarbonate siloxane copolymer orstructural units thereof are integers representing the number ofrepeating units of the Formulas. The integer x is at least 1 andtypically falls within the same range as E, as previously described. Theinteger y is at least one and typically less than 15 or 10. In someembodiments, z ranges from 50 to 400.

According to US2013/0186799, incorporated herein by reference, Formula Vprovides the molecular structure of the polycarbonate (PC) siloxaneresin LEXAN™ EXL 1414T resin.

Since the LEXAN™ copolymers are (e.g. transparent) thermally processiblethermoplastic resins, such copolymers can be used to make liquidrepellent components (e.g. liquid reservoir, liner, lid) of the sprayapplication system utilizing various thermal processing techniques suchas injection molding and thermoforming.

In some embodiments, at least the repellent surface layer is preparedfrom a (e.g. transparent) siloxane copolymer having a melt flow rate ofat least 2.5, 5 or 10 g/10 minutes at 300° C./1.2 kgf (ASTM D1238) andtypically no greater than 30, 25 or 20 g/10 minutes. Mixtures ofpolycarbonate siloxane copolymers of different flow properties can beused to achieve the overall desired flow property. Highly crosslinked(e.g. thermoset) siloxane materials generally do have melt flow indexesin the ranges just described.

The tensile strength of the siloxane copolymer is typically at least 40,45, 50, 55, or 60 MPa. Further, the siloxane copolymer can have a lowelongation at break of less than 10% or 5%. In some embodiments, thesiloxane copolymer has a tensile modulus of at least 1000, 1500, or 2000MPa ranging up to 2500 MPa. The tensile and elongation properties can bemeasured according to ASTM D-638 (e.g. at a rate of 50 mm/min).

PDMS generally has a melting point of about −40° C. and a glasstransition temperature (Tg) of about −125° C. Siloxane copolymers canhave melting point and glass transition temperatures greater than 0° C.or greater than 25° C. In some embodiments, the siloxane copolymer has amelt temperature of at least 100° C., 150° C., 200° C., 250° C., or 300°C. and typically no greater than 350° C. or 400° C. In some embodiments,the siloxane copolymer has a Tg of at least 50° C., 75° C., 100° C.,125° C., or 150° C. and typically no greater than 175° C. or 200° C.Unless specified otherwise, thermal properties can be determined byDifferential Scanning calorimetry (DSC).

In some embodiments, the repellent surface can be prepared by providinga repellent surface layer on a spray application system component (e.g.liquid reservoir, liner, lid) formed by application of an organicsolvent-coating composition comprising siloxane material such as apolycarbonate-siloxane copolymer to a spray application systemcomponent.

Various organic polymeric binders can be utilized. Although fluorinatedorganic polymeric binders can also be utilized, fluorinated organicpolymeric binders are typically considerably more expensive thannon-fluorinated binders. Further, non-fluorinated organic polymericbinders can exhibit better adhesion to polymeric components (e.g.reservoir, liner, or lid) of the spray application system.

Suitable non-fluorinated binders include for example polystyrene,atactic and syndiotactic polystyrene, acrylic (i.e. poly(meth)acrylate),polyester, polyurethane (including polyester type thermoplasticpolyurethanes “TPU”), polyolefin (e.g. polyethylene), and polyvinylchloride. Many of the polymeric materials that the component (e.g.reservoir, liner, or lid) of the spray application system can bethermally processed from, as will subsequently be described, can be usedas the non-fluorinated organic polymeric binder of an (e.g. organicsolvent) coating composition. However, in typical embodiments, thenon-fluorinated organic polymeric binder is a different material thanthe polymeric material of the component. In some embodiments, theorganic polymeric binder typically has a receding contact angle withwater of less than 90, 80, or 70 degrees. Thus, the binder is typicallynot a siloxane (e.g. PDMS) material.

In some embodiments, the (e.g. non-fluorinated) organic polymeric binderis a film-grade resin, having a relatively high molecular weight.Film-grade resins can be more durable and less soluble in an organicsolvent that may be present in the liquid (e.g. paint) being repelled.In other embodiments, the (e.g. non-fluorinated) organic polymericbinder can be a lower molecular weight film-forming resin. Film-formingresins can be more compliant and less likely to affect thecollapsibility of a liquid (e.g. paint) reservoir or liner. Viscosityand melt flow index are indicative of the molecular weight. Mixtures of(e.g. non-fluorinated) organic polymeric binder can also be used.

In some embodiments, the film-grade (e.g. non-fluorinated) organicpolymeric binder typically has a melt flow index of at least 1, 1.5, 2,2.5, 3, 4, or 5 g/10 min at 200° C./5 kg ranging up to 20, 25, or 30g/10 min at 200° C./5 kg. The melt flow index can be determinedaccording to ASTM D-1238. The tensile strength of the (e.g.non-fluorinated) organic polymeric binder is typically at least 40, 45,50, 55, or 60 MPa. Further, the (e.g. non-fluorinated) organic polymericbinder can have a low elongation at break of less than 10% or 5%. Thetensile and elongation properties can be measured according to ASTMD-638. Such film-grade (e.g. non-fluorinated) organic polymeric bindersjust described can also be suitable for use as a thermally processiblepolymer of the spray application system component (e.g. reservoir,liner, lid).

In other embodiments, the (e.g. non-fluorinated) organic polymericbinders have a lower molecular weight and lower tensile strength thanfilm-grade polymers. In one embodiment, the melt viscosity of the (e.g.non-fluorinated) organic polymeric binders (as measured by ASTMD-1084-88) at 400° F. (204° C.) ranges from about 50,000 to 100,000 cps.In another embodiment, the molecular weight (Mw) of the (e.g.non-fluorinated) organic polymeric binder is typically at least about1000, 2000, 3000, 4000, or 5000 g/mole ranging up to 10,000; 25,000;50,000; 75,000; 100,000; 200,000; 300,000; 400,000, or 500,000 g/mole.In some embodiments, the (e.g. non-fluorinated) organic polymeric binderhas a tensile strength of at least 5, 10, or 15 MPa ranging up to 25, 30or 35 MPa. In other embodiments, the (e.g. non-fluorinated) organicpolymeric binder has a tensile strength of at least 40, 45, or 50 MParanging up to 75 or 100 MPa. In some embodiments, the (e.g.non-fluorinated) organic polymeric binder has an elongation at breakranging up to 25, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900 or1000% or higher. In some embodiments, the (e.g. non-fluorinated) organicpolymeric binder has a Shore A hardness of at least 50, 60, 70, or 80ranging up to 100.

In some embodiments, the (e.g. non-fluorinated) organic polymeric binderis selected such that it is (e.g. mechanically) compliant at the usetemperature of the coated substrate or article.

In this embodiment, the (e.g. non-fluorinated) organic polymeric binderhas a glass transition temperature (Tg) as can be measured by DSC ofless than 0° C. or 32° F. In some embodiments, the (e.g.non-fluorinated) organic polymeric binder has a glass transitiontemperature (Tg) of less than 20° F., 10° F., 0° F., −10° F., −20° F.,−30° F., −40° F., −50° F., −60° F., −70° F., or −80° F. In someembodiments, the (e.g. non-fluorinated) organic polymeric binder has aTg of at least −130° C. The selection of (e.g. non-fluorinated) organicpolymeric binder can contribute to the durability of the repellentsurface.

In typical embodiments, the non-fluorinated organic polymeric bindertypically does not form a chemical (e.g. covalent) bond with thesiloxane (e.g. PDMS) material as this may hinder the migration of thesiloxane (e.g. PDMS) material to the outermost surface layer.

In some embodiments, the (e.g. non-fluorinated) organic polymeric binderis not curable, such as in the case of alkyd resins. An alkyd resin is apolyester modified by the addition of fatty acids and other components.They are derived from polyols and a dicarboxylic acid or carboxylic acidanhydride. Alkyds are the most common resin or “binder” of mostcommercial “oil-based” paints and coatings.

In some embodiments, the selection of the non-fluorinated polymericbinder can affect the concentration of siloxane (e.g. PDMS) materialthat provides the desired liquid (e.g. paint) repellency properties.

The siloxane (e.g. PDMS) polymers or compositions comprising a siloxane(e.g. PDMS) material and a non-fluorinated organic polymeric binder canbe dissolved, suspended, or dispersed in a variety of organic solventsto form coating compositions suitable for use in coating thecompositions onto a substrate or component of a spray applicationsystem. The organic coating compositions typically contain at leastabout 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%,98%, 99% organic solvent or greater, based on the weight of the coatingcomposition. The coating compositions typically contain at least about0.01%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15% orgreater solids of (e.g. non-fluorinated) organic polymeric binder andsiloxane (e.g. PDMS) material, based on the total weight of the coatingcomposition. However, the coating composition can be provided as aconcentrate with an even higher amount of solids, e.g. 20, 30, 40, or 50wt.-% solids. Suitable solvents include for example alcohols, esters,glycol ethers, amides, ketones, hydrocarbons, chlorohydrocarbons,hydrofluorocarbons, hydrofluoroethers, chlorocarbons, and mixturesthereof. In some embodiments, the coating composition is an aqueoussuspension, emulsion, or solution comprising at least 50 wt.-% orgreater water and an organic cosolvent.

In one embodiment, the coating composition may contain 5 wt.-% of lowdensity polyethylene binder (such as the NA217000 LDPE or Marflex 1122LDPE described in the forthcoming examples) dissolved is 95 wt.-% ororganic solvent, such as xylene, toluene, or dichloroethylene. Thecoating composition may further contain 3 wt.-% of siloxane material(such as SMA described in the forthcoming examples). Otherconcentrations of binder and siloxane material can be utilized providedthe desired liquid repellency properties are attained.

The coating compositions may contain one or more additives provided theinclusion of such does not detract from the liquid (e.g. paint)repellent properties.

The coating compositions can be applied to a substrate or component bystandard methods such as, for example, spraying, padding, dipping, rollcoating, brushing, or exhaustion (optionally followed by the drying ofthe treated substrate to remove any remaining water or organic solvent).The substrate can be in the form of sheet articles that can besubsequently thermally formed into a liquid (e.g. paint) reservoir,liner or lid. When coating flat substrates of appropriate size,knife-coating or bar-coating may be used to ensure uniform coatings ofthe substrate.

The moisture content of the organic coating composition is preferablyless than 1000, 500, 250, 100, or 50 ppm. In some embodiments, thecoating composition is applied to the substrate at a low relativehumidity, e.g. of less than 40%, 30%, or 20% at 25° C.

The coating compositions can be applied at an amount sufficient toachieve the desired repellency properties. Coatings as thin as 250, 300,350, 400, 450, or 500 nm ranging up to 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or5 microns can provide the desired repellency. However, thicker coatings(e.g., up to about 10, 15, 20 microns or more) can also be used. Thickercoatings can be obtained by applying to the substrate a single thickerlayer of a coating composition that contains a relatively highconcentration of solids. Thicker coatings can also be obtained byapplying successive layers to the substrate.

In another embodiment, the siloxane (e.g. PDMS) material can be combinedwith a thermally processible (e.g. thermoplastic) polymer and then meltprocessed into a surface layer, substrate, or component such as a liquid(e.g. paint) repellent reservoir, liner or lid. In this embodiment, thesiloxane (e.g. PDMS) material typically migrates to the surface forminga surface layer with a high concentration of siloxane material relativeto the total amount of siloxane material and thermally processiblepolymer.

In typical embodiments, the amount of siloxane (e.g. PDMS) material(melt additive) is at least about 0.05, 0.1, 0.25, 0.5, 1.5, 2.0 or 2.5wt.-% and in some embodiments, at least about 3.0, 3.5, 4.0, 4.5 or 5wt.-%. The amount of siloxane material is typically no greater than 25,20, 15, or 10 wt.-% of the sum of the siloxane (e.g. PDMS) material(melt additive) and thermally processible polymer.

To form a polymer blend by melt processing, the siloxane material canbe, for example, mixed with pelletized, granular, powdered or otherforms of the thermally processible polymer and then melt processed byknown methods such as, for example, molding or melt extrusion. Thesiloxane (e.g. PDMS) material can be mixed directly with the thermallyprocessible polymer or it can be mixed with the (thermally processible)polymer in the form of a “master batch” (concentrate) of the siloxane(e.g. PDMS) material in the (same or similar) polymer as the thermallyprocessible polymer. If desired, an organic solution of the siloxane(e.g. PDMS) material can be mixed with powdered or pelletized polymer,followed by drying (to remove solvent) and then melt processing.Alternatively, the siloxane (e.g. PDMS) composition can be added to thepolymer melt to form a mixture or injected into a molten polymer streamto form a blend immediately prior to extrusion or molding into articles.

In some embodiments, the melt processible (e.g. thermoplastic) polymeris a polyolefin, polyester, polyamide, polyurethane, polycarbonate,polystyrene, poly(alkyl acrylate), or polyacrylate. The thermoplasticpolymer preferably is a polyolefin, mixture or blend of one or morepolyolefins, a polyolefin copolymer, mixture of polyolefin copolymers,or a mixture of at least one polyolefin and at least one polyolefincopolymer.

The thermoplastic polymer is more preferably a polyolefin polymer orcopolymer wherein the polymer unit or copolymer unit is ethylene,propylene, butylene, hexene or mixtures thereof. Thus the polyolefin ispreferably polypropylene, polyethylene, polybutylene, polyhexylene or ablend or copolymer thereof. Oher polyolefins include poly-α-olefins, andcopolymers thereof, including low density polyethylene (LDPE), highdensity polyethylene (HDPE), linear low density polyethylene (LLDPE),ultra-high density polyethylene (UHDPE), and polyethylene-polypropylenecopolymers, as well as polyolefin copolymers having non-olefin content(that is, content derived from monomers that are not olefins). Thenon-olefin content of polyolefin polymers employed in some embodimentsis not particularly limited, but includes, for example, 1-5 wt % ofacrylic acid, or methacrylic acid functionality, including sodium, zinc,or calcium salts of the acid functionality; 1-5 wt % of an anhydridefunctionality, such as maleic anhydride, or the correspondingring-opened carboxylate functionality; and the like. In someembodiments, blends of polyolefins containing non-polyolefin content areblended at various ratios with polyolefins in order to provide atargeted level of non-olefin content.

In one embodiment, the thermoplastic polymer is polyethylene having amelting point ranging from 90-140° C. such as available from ChevronPhillips under the trade designation “MarFlex 1122 Polyethylene”.

The siloxane melt additives are generally a solid at room temperature(e.g. 25° C.) and at the use temperature of the spray application systemcomponent, which commonly ranges from 40° F. to 120° F. The siloxane(e.g. PDMS) material and thermally processible polymer are selected suchthat the siloxane material is typically molten at the melt processingtemperature of the mixture. In some embodiments, the siloxane materialhas a melt temperature no greater than 200, 190, 180, 170, or 160° C. Inother embodiments, the melt temperature may be higher.

The melt processible polymer of the repellent surface and/or component(e.g. reservoir, liner, lid) may further contain non-siloxane slipagents, anti-blocks (e.g. silica, talc) antioxidants, tints, antistaticagents, light stabilizers, clarifiers, nucleating agents, and otheradditives known in the art. Clarifiers typically increase the clarity byreducing the size of the spherulites. Smaller spherulites allow morelight through the polymer, which decreases the haze of the part. Unlikenucleating agents, clarifiers are transparent, which also helps todecrease haze values.

Extrusion can be used to form polymeric films. In film applications, afilm forming polymer is simultaneously melted and mixed as it isconveyed through the extruder by a rotating screw or screws and then isforced out through a slot or flat die, for example, where the film isquenched by a variety of techniques known to those skilled in the art.The films optionally are oriented (after being cast) prior to quenchingby drawing or stretching the film at elevated temperatures in themachine and/or transverse directions simultaneously or sequentially.

Molded articles are produced by pressing or by injecting molten polymerfrom a melt extruder as described above into a mold where the polymersolidifies. Typical melt forming techniques include injection molding,blow molding, compression molding and extrusion, and are well known tothose skilled in the art. The molded article is then ejected from themold and optionally heat-treated to effect migration of the polymeradditives to the surface of the article.

In some embodiments, a molded component with a liquid-repellent surfacemay be made using molding processes (e.g. co-injection molding orbi-injection molding) in which two different resins are injected into amold through the same gate or different gates to form an integralliquid-repellent skin layer over a core layer in a single moldingprocess. For example, the first of the two resins could be a polyolefin,and the second of the two resins could be a polyolefin to which a neatmelt additive or melt additive masterbatch has been added.

After melt processing, an annealing step can be carried out to enhancethe development of repellent characteristics. The annealing steptypically is conducted below or above the melt temperature of thepolymer for a sufficient period of time. The annealing step can beoptional.

The repellent surface layer described herein can be provided on a widevariety of organic or inorganic components.

In some embodiments, different components are coated with differentsolid materials. In other embodiments, the surface of one portion of acomponent can comprise one type of a solid liquid (e.g. paint) repellentmaterial and another surface portion can comprise a different type ofsolid material. Likewise, the surface of one portion of a component cancomprise one type of a solid liquid (e.g. paint) repellent material andanother surface portion can comprise a different liquid (e.g. paint)repellent material.

In typical embodiments, the entire surface of the component (e.g.reservoir, liner or lid) of the spray application system that normallycomes in contact with a liquid (e.g. paint) comprises a liquid (e.g.paint) repellent surface as described herein. In other embodiments, onlya portion of the surface of the component (e.g. reservoir, liner or lid)of the spray application system that normally comes in contact with aliquid (e.g. paint) comprises a liquid (e.g. paint) repellent surface asdescribed herein. This latter embodiment is still beneficial relative tocomponents lacking a liquid (e.g. paint) repellent surface.

Suitable polymeric materials for components include, but are not limitedto, polyesters (e.g., polyethylene terephthalate or polybutyleneterephthalate), polycarbonates, acrylonitrile butadiene styrene (ABS)copolymers, poly(meth)acrylates (e.g., polymethylmethacrylate, orcopolymers of various (meth)acrylates), polystyrenes, polysulfones,polyether sulfones, epoxy polymers (e.g., homopolymers or epoxy additionpolymers with polydiamines or polydithiols), polyolefins (e.g.,polyethylene and copolymers thereof or polypropylene and copolymersthereof), polyvinyl chlorides, polyurethanes, fluorinated polymers,cellulosic materials, derivatives thereof, and the like.

In some embodiments, where increased transmissivity is desired, thepolymeric component can be transparent. The term “transparent” meanstransmitting at least 85 percent, at least 90 percent, or at least 95percent of incident light in the visible spectrum (wavelengths in therange of 400 to 700 nanometers). Transparent components may be coloredor colorless.

Suitable inorganic substrates include metals and siliceous materialssuch as glass. Suitable metals include, for example, pure metals, metalalloys, metal oxides, and other metal compounds. Examples of metalsinclude, but are not limited to, chromium, iron, aluminum, silver, gold,copper, nickel, zinc, cobalt, tin, steel (e.g., stainless steel orcarbon steel), brass, oxides thereof, alloys thereof, and mixturesthereof.

The siloxane materials described herein can render the coated surfacehydrophobic. The terms “hydrophobic” and “hydrophobicity” refer to asurface on which drops of water or aqueous liquid exhibit an advancingand/or receding water contact angle of at least 50 degrees, at least 60degrees, at least 70 degrees, at least 80 degrees, at least 90 degrees,at least 95 degrees, or at least 100 degrees.

In some embodiments, the advancing and/or receding contact angle of therepellent surface of the substrate or component with water may increase,relative to the substrate or component lacking a liquid (e.g. paint)repellent surface, by at least 10, 15, 20, 25, 30, 35, 40 degrees. Insome embodiments, the receding contact angle with water may increase byat least 45, 50, 55, 60, or 65 degrees.

In some embodiments, the (e.g. siloxane) materials described herein,provide a surface that exhibits an advancing and/or receding contactangle with water of at least 105, 110, or 115 degrees. The advancingand/or receding contact angle with water is typically no greater than135, 134, 133, 132, 131, or 130 degrees and in some embodiments, nogreater than 129, 128, 127, 126, 125, 124, 123, 122, 121, or 120degrees. The difference between the advancing and/or receding contactangles (contact angle hysteresis (“CAH”)) with water of the liquidrepellent surface layer can be at least 5, 10, 15, 20, 25, 30, 35, 40,45, or 50 degrees. Favorably the difference between the advancing andreceding contact angle with water of the surface treated hydrophobiclubricant impregnated porous surface, as well as the other (e.g. solid)materials described herein is no greater than 15, 14, 13, 12, 11, 10, 9,8, 7, 6, 5, 4, 3, 2, or 1 degree. As the difference between theadvancing and/or receding contact angle with water increases, the tiltangle needed to slide or roll off a (e.g. water or paint) droplet from aplanar surface increases. One of ordinary skill appreciates thatdeionized water is utilized when determining contact angles with water.

The contact angle of the liquid (e.g. paint) repellent surface of thesubstrate or component can also be evaluated with other liquids insteadof water. For example, since paints, such as water-based automobilepaints, often comprise 2-n-butoxyethanol, the contact angle of theliquid (e.g. paint) repellent surface with a solution of 10% by weight2-n-butoxyethanol and 90% by weight deionized water can also be ofimportance. In some embodiments, the advancing contact angle with such2-n-butoxyethanol solution is at least 45, 46, 47, 48, 49, 50, 51, 52,53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70degrees and in some embodiments at least 75 or 80 degrees. In someembodiments, the receding contact angle with such 2-n-butoxyethanolsolution is at least 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,48, 49, 50, 55, 60, 65, or 70 degrees. In some embodiments, theadvancing and/or receding contact angle of the liquid (e.g. paint)repellent surface of the substrate or component with a solution of 10%by weight 2-n-butoxyethanol and 90% by weight deionized water is nogreater than 100, 95, 90, 85, 80, or 75 degrees.

In another embodiment, the contact angle of the liquid (e.g. paint)repellent surface of the substrate or component with hexadecane is atleast 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, or 75 degrees. Theadvancing contact angle with hexadecane is typically at least 45, 50,55, 60, 65, 70, 75, 80, or 84 degrees. In typical embodiments, thereceding or advancing contact angle with hexadecane is no greater than85 or 80 degrees.

The (e.g. siloxane) materials described herein can be used to impart orenhance (e.g. aqueous) liquid repellency of a variety of substrates.

The term “aqueous” means a liquid medium that contains at least 50, 55,60, 65, or 70 wt-% of water. The liquid medium may contain a higheramount of water such as at least 75, 80, 85, 90, 95, 96, 97, 98, 99, or100 wt.-% water. The liquid medium may comprise a mixture of water andone or more water-soluble organic cosolvent(s), in amounts such that theaqueous liquid medium forms a single phase. Examples of water-solubleorganic cosolvents include for example methanol, ethanol, isopropanol,2-methoxyethanol, (2-methoxymethylethoxy)propanol, 3-methoxypropanol,1-methoxy-2-propanol, 2-butoxyethanol, ethylene glycol, ethylene glycolmono-2-ethylhexylether, tetrahydrofuran, 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate, tetraethylene glycol di(2-ethylhexoate),2-ethylhexylbenzoate, and ketone or ester solvents. The amount oforganic cosolvent does not exceed 50 wt-% of the total liquids of thecoating composition. In some embodiments, the amount of organiccosolvent does not exceed 45, 40, 35, 30, 25, 20, 15, 10 or 5 wt.-%organic cosolvent. Thus, the term aqueous includes (e.g. distilled)water as well as water-based solutions and dispersions such as paint.

In some embodiments, the aqueous (e.g. paint) “ready to spray”dispersions, e.g. paint, described herein may comprise at least 5, 10,or 15 wt.-% solids with the remainder being aqueous liquid medium. Insome embodiments, the aqueous (e.g. paint) “ready to spray” dispersions,e.g. paint, described herein may comprise at least 20, 25, 30, or 35wt.-% solids with the remainder being aqueous liquid medium. Further, insome embodiments, the aqueous (e.g. paint) dispersions may be aconcentrate comprising at least 40, 45, 50, 55, 60, 65, 70, 75, 80, or85 wt.-% solids with the remainder being aqueous liquid medium. Suchconcentrates are generally diluted to prepare an aqueous (e.g. paint)“ready to spray” dispersion.

In some embodiments, the (e.g. solid) materials described herein canimpart a degree of aqueous liquid repellency such that no greater than40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, or 1% of the repellent surfacearea comprises an aqueous test liquid, such as paint, after use of thespray application system or after holding the repellent surfacevertically for a specified duration of time (e.g. 30 seconds-5 minutesor 30 minutes) and visually determining (in the absence of a microscope)the amount of aqueous liquid (e.g. paint). In some embodiments,polypropylene glycol (400 Mw), butoxyethanol, or a 50 wt. % aqueoussolution of butoxyethanol can be used as a test liquid.

In some embodiments, the porous layer impregnated lubricant, as well asthe other (e.g. solid) materials described herein can impart a degree ofliquid repellency such that the mass of retained aqueous liquid (e.g.paint) is no greater than 0.01 g/cm², 0.005 g/cm², 0.001 g/cm², or0.0005 g/cm². In some embodiments, polypropylene glycol (400 Mw),butoxyethanol, or a 50 wt. % aqueous solution of butoxyethanol can beused as a test liquid.

The paint repellency can be evaluated according to any one orcombination of test methods described herein utilizing a test paint.Various aqueous-based automotive paints were found to be repelled by thesurfaces described herein such as PPG ENVIROBASE HIGH PERFORMANCE T409,SIKKENS AUTOWAVE, SPIES HECKER PERMAHYD HI-TEC BASE COAT 480, andGLASURIT ADJUSTING BASE 93-E3. Unless specified otherwise, the testpaint for determining paint repellency according to the test methodsdescribed herein was PPG Envirobase automobile paint mixed tospecification containing 90 weight % ENVIROBASE HIGH PERFORMANCE T409DEEP BLACK and 10 weight % ENVIROBASE HIGH PERFORMANCE T494 PAINTTHINNER, available from PPG Industries, Pittsburgh Pa. or available from3M, St. Paul, Minn.

The liquid (e.g. paint) repellent surface is preferably durable suchthat the liquid (e.g. paint) repellency is retained for a sufficientamount of time (e.g. the normal duration of time a (e.g. disposable)liquid (e.g. paint) reservoir or liner is utilized). In someembodiments, the liquid (e.g. paint) repellency is retained aftersurface abrasion testing (according to the test method described in theexamples). In some embodiments, the liquid (e.g. paint) repellency maydiminish to some extent, yet remains highly repellent after surfaceabrasion testing. Thus, after surface abrasion testing the contactangles or paint repellency meet(s) the criteria previously described.

The spray application system described herein can be utilized to applyan aqueous liquid mixture, such as paint.

As used herein, the term “paint” refers to a composition having anaqueous liquid medium, as previously described, and a polymeric (e.g.latex) binder dispersed in the aqueous liquid medium. Common polymericbinders utilized in paint include acrylic polymers, alkyd polymers,urethane polymers, epoxy polymers, and combinations thereof. In someembodiments, the (e.g. base coat) paint may comprise a combination ofacrylic and alkyd polymers. In other embodiments, the (e.g. clear coat)paint may comprise hexamethylene isocyanate oligomers and/or cyclohexylisocyanate oligomers at concentrations ranging from about 20 to 40 wt-%for “ready to spray” compositions.

In the absence of opacifying pigment(s), such as titanium dioxide,silica, carbon black, etc. or other colorant (i.e. pigment or dye otherthan black or white) the paint may be characterized as a “clear coat”.Paints that further comprise opacifying pigment(s), yet not coloredpigments may be characterized as primers. Further, paints that furthercomprise both opacifying pigment(s) and colorant(s) may be characterizedas base coats.

Whereas clear coats are generally free of opacifying pigments andcolorants, primers and base coats typically comprise at least 10, 15,20, 25 or 30 wt.-% or greater of opacifying pigment(s) such as titaniumdioxide. Base coats further comprise colorants at variousconcentrations. In some embodiments, the paint comprises 5 to 25 wt.-%of colorants.

The liquid medium may comprise relatively small concentrations ofvolatile organic solvents. For example, the volatile organic content ofwater-based flat architectural paint, water-based automobile primer, andwater-based clear coat is typically no greater than 250 grams/liter andin some embodiments no greater than 200 grams/liter, 150 grams/liter,100 grams/liter, or 50 grams/liter. The VOC content may be higher,ranging from at least 275, 300, or 325 grams/liter up to 500grams/liter, particularly for automobile base coat. In some embodiments,the VOC content is no greater than 450 or 425 grams/liter. Paintreferred to as no-VOC typically may contain 5 grams/liter or less ofvolatile organic solvents. As used herein, VOC is any organic compoundhaving a boiling point less than or equal to 250° C. measured at astandard atmospheric pressure of 101.3 kPa.

As the concentration of colored pigment(s) increases, the concentrationof (e.g. volatile) organic solvents present for the purpose ofdissolving and dispersing such colored pigment(s) can also increase.Further, (e.g. volatile) organic solvents can also be utilized to lowerthe viscosity of the paint. Viscosity will vary with the thinner levelchosen. However, in some embodiments, the viscosity of the “ready tospray” paint at 20° C. ranges from 50 to 100 cps.

The paint may comprise water-soluble organic solvents such as alcohols(e.g. alkylene glycol alkyl ether). For example, the paint may comprise2-butoxyethanol (ethylene glycol monobutyl ether), having a boilingpoint of 171° C. (340° F.); butoxypropan-2-ol (propylene glycol n-butylether), having a boiling point of 171° C. (340° F.);2-(2-butoxyethoxy)ethanol (diethylene glycol monobutyl ether), having aboiling point of 230° C. (446° F.); and combinations thereof. The paintmay comprise one or more of such alcohols at a total concentration of atleast 5 wt.-% ranging up to 10, 15, 20, or 25 wt.-%.

The paint may further comprise other solvents that may be characterizedas “exempt” solvents, i.e. not causing the formation of ground levelozone (smog), according to environmental chemists. Representativeexamples include acetone, ethyl acetate, tertiary butyl acetate (TBAc),and isopropanol.

When the spray application system described herein is utilized to applyan aqueous liquid mixture, such as paint, the method may compriseapplying more than one coat of the same or different paint compositions.For example, in one embodiment, the method may comprise applying one ormore coats of a primer or sealer. In another embodiment, the method maycomprise applying one or more coats of a (e.g. colored) base coat. Inanother embodiment, the method may comprise applying one or more coatsof a clear coat. The method may comprise applying a combination ofprimer, sealer, base coat, and/or clear coat. The method is particularlyadvantageous for use with (e.g. automobile) base coats that aresubstantially more expensive than primers, sealers and clear coats.

In some embodiments, 3-4 coats may be applied (e.g. to an automobilepanel) wherein each coat, or in other words “film build per wet coat”ranges in thickness from 0.80 to 1.0 mils. Upon drying this can producea dried film build ranging from about 0.10 to 0.20 mils.

In some embodiments, each coat of the method utilizes an aqueous paint.In other embodiments, at least one coat may be an organic solvent basedpaint, i.e. a paint comprising greater than 50 wt-% organic solvent thatmay not form a single phase with water. Organic solvent-based paintstypically do not contain any water. For example, solvent-based clearcoats may contain organic polar and non-polar solvents such as xylene,acetone, naphtha, alkyl benzene, toluene, heptan-2-one, and the like ata total organic solvent concentration ranging from at least 50 wt.-%, or60 wt.-% up to about 75 wt.-% or greater.

In one embodied method, a solvent based clear coat is applied to a driedwater based base coat.

When the paint comprises organic solvent, the non-fluorinated polymericbinder and/or siloxane (e.g. PDMS) material may be selected to exhibitno solubility or only trace solubility with the organic solvent(s) ofthe paint, e.g., a solubility of 0.01 grams/liter or 0.001 grams/literor less.

Alternatively or in combination with having trace solubility, thenon-fluorinated polymeric binder and/or the siloxane (e.g. PDMS)material may be selected such that it is compatible with the paint andpaint application methods. The non-fluorinated polymeric binder and/orsiloxane (e.g. PDMS) material may be present in the paint at higherconcentrations, i.e. greater than 0.01 grams/liter, or greater than 0.1grams/liter, or greater than 0.25 grams/liter, or greater than 0.5grams/liter; yet still be compatible with the paint and paintapplication methods. In some embodiments, non-fluorinated polymericbinder and/or siloxane (e.g. PDMS) material may function as a paintadditive and be present in the paint at concentrations ranging fromabout 0.5 grams/liter to 1, 1.5, 2, 2.5, or 3 wt-% of the paint.

There are various approaches that can be taken to determine thecompatibility of the non-fluorinated polymeric binder and/or siloxane(e.g. PDMS) material with the paint.

In one approach, when opposing major surface layers of the dried paintcomprise substantially the same concentration (difference of less than10, 5 or 1% relative to the major surface having the higherconcentration) of non-fluorinated polymeric binder and/or siloxane (e.g.PDMS) material, such materials can be characterized as chemicallycompatible with the paint.

In another approach, the siloxane (e.g. (PDMS) material may besufficiently compatible with the paint such that the presence thereofdoes not affect the inter-layer adhesion of a painted substrate. Thiscan be evaluated according to Standard Test Method for MeasuringAdhesion by Tape Test (ASTM D3359-09). When the cross-hatch adhesion issubstantially the same relative to a control of the same paint in theabsence of the lubricant (or the combination of lubricant andhydrophobic layer), the presence of the lubricant (or the combination oflubricant and hydrophobic layer) can be characterized as not affectingthe inter-layer adhesion. Typically, 90, 95, or 100% of the paint isretained after cross-hatch adhesion testing according to ASTM D3359-09.The non-fluorinated polymeric binder and/or siloxane (e.g. PDMS)material may be sufficiently compatible with the paint such that thepresence thereof does not affect the inter-layer adhesion of a paintedsubstrate.

In yet another approach, the non-fluorinated polymeric binder and/orsiloxane (e.g. PDMS) material may be sufficiently compatible with thepaint such that the siloxane (e.g. PDMS) material does not affect themethod of applying the paint. For example, additional coats of the samepaint can be uniformly applied at a sufficient film build as previouslydescribed. In yet another example, additional coats of a different paint(e.g. a clear coat applied to a dried base coat) can be uniformlyapplied at a sufficient film build as previously described. Lack ofuniformity across the painted panel or substrate can typically bevisually detected by observing the occurrence of “fisheyes” or otherincompatibility-related coating defects while applying the paint and/orby uneven gloss and/or color that can be measured after the appliedpaint has dried.

The liquid repellent surface (e.g. layer) of the component (e.g. liquidreservoir, liner, or lid) can be provided by one of the embodiedsiloxane materials previously described or any suitable combination ofsuch siloxane materials with each other, or any suitable combination ofsuch siloxane material(s) with the lubricant impregnated materialsand/or fluorinated materials described in WO2016/069674. Further, one ofthe components can have a different embodied material than anothercomponent. For example, the reservoir and/or lid may comprise Lexan™1414T; whereas the liner comprises a thermally processible polymer and asiloxane copolymer melt additive.

Unless specified otherwise, the following definitions are applicable tothe presently described invention.

The recitation of any numerical range by endpoints is meant to includethe endpoints of the range, all numbers within the range, and anynarrower range within the stated range.

The term “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

The term “and/or” means either or both. For example, the expression “Aand/or B” means A, B, or a combination of A and B.

The term “alkylene” refers to a divalent group that is a radical of analkane and includes groups that are linear, branched, cyclic, bicyclic,or a combination thereof. The alkylene group typically has 1 to 30carbon atoms. In some embodiments, the alkylene group has 1 to 20 carbonatoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbonatoms.

The term “alkoxy” refers to refers to a monovalent group having an oxygroup bonded directly to an alkyl group.

The term “aryl” refers to a monovalent group that is aromatic andcarbocyclic. The aryl has at least one aromatic ring and can have one ormore additional carbocyclic rings that are fused to the aromatic ring.Any additional rings can be unsaturated, partially saturated, orsaturated. Aryl groups often have 6 to 20 carbon atoms, 6 to 18 carbonatoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbonatoms.

The term “fluorinated” refers to a group or compound that contains atleast one fluorine atom attached to a carbon atom. Perfluorinatedgroups, in which there are no carbon-hydrogen bonds, are a subset offluorinated groups.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

Test Methods

IR data was obtained using a Nicolet 6700 Series FT-IR spectrometer(Thermo Scientific, Waltham, Mass.).

Method for Contact Angle Measurements

Water contact angles were measured using a Ramé-Hart goniometer(Ramé-Hart Instrument Co., Succasunna, N.J.). Advancing (θ_(adv)) andreceding (θ_(rec)) angles were measured as water was supplied via asyringe into or out of sessile droplets (drop volume˜5 μL). Measurementswere taken at 2 different spots on each surface, and the reportedmeasurements are the averages of the four values for each sample (aleft-side and right-side measurement for each drop).

Contact angles were also evaluated in the same manner using a 90/10 bywt. mixture of water/butoxyethanol instead of water.

Test Method 1 for Paint Repellency Evaluation

Test surfaces were submerged in the PPG Envirobase paint and allowed tosit overnight. The test substrates were then removed from the paint andheld vertically for 5 min to allow the paint to potentially flow off ofthe coating. The fraction (expressed as a percentage) of the surfacethat was still covered by paint was estimated by visual inspection.

Test Method 2 for Paint Repellency Evaluation—

Sample components or pieces thereof measuring approximately 4 cm×4 cmhaving a liquid repellent surface can be prepared as described below andthe initial masses measured. The PPG Envirobase paint was pipetted ontothese film pieces until the entire surface was covered with paint. Thepainted film samples were then turned vertically for 5 minutes to allowpaint to drain off of the surface. The masses of the drained film pieceswere measured to determine the mass of paint residue remaining on thesurface. The drained pieces were also visually inspected to estimate thefraction (expressed as a percentage) of the film surface that remainscoated by the paint.

Test Method 3 for Paint Repellency Evaluation:

70 g of PPG Envirobase automotive paint was poured into the liner havingthe repellent interior surface and a comparative liner (CE. F) that wasthe same liner without the repellent interior surface. The liners weremanually shaken and rotated to ensure that the paint contacted all ofthe container side walls. The paint was then poured out of the liners,and the liners were placed upside down for 5 minutes (liner withrepellent interior) or other specified period of time to allow more ofthe paint to drain. The liners were each reweighed and the mass ofretained paint was calculated.

Test Method 4 for Paint Repellency Evaluation:

A single drop of the (e.g. PPG Envirobase) paint, approximately 0.2 mL,was applied at 21° C. to a central portion of the (e.g. repellentsurface of the) sample (7.5 cm by 5.0 cm coated glass microscope slide).The sample (e.g. glass slide) was immediately orientated vertically. Ifthe paint drop slid down the glass slide, it was denoted “Pass”, if not“Fail”. In some samples that passed, a thin strip of paint (<20% thethickness of the initial drop) or a few small droplets of paint remainedon the surface after the paint drop slid down.

Test Method 5 for Paint Repellency Evaluation:

The entire non-repellent surface of the sample (i.e. uncoated side ofthe 7.5 cm by 5.0 cm glass slide) was masked with tape, obtained from 3MCompany under the trade designation “SCOTCHBLUE PAINTERS TAPE”. Thesample (glass slide) was then immersed in the (e.g. PPG Envirobase)paint to a depth of 3.5 cm for 10 minutes at 21° C. (or in other wordsabout half the coated surface was immersed). The sample (glass slide)was removed from the diluted paint, orientated vertically for 30seconds, and the masking tape removed. The paint remaining on theimmersed coated surface was then visually estimated and expressed aspercentage of retained paint coverage.

Test Method 6 for Paint Repellency Evaluation:

A sample of sufficient size (2.8 by 3.2 cm) was weighed. The entirenon-repellent surface of the sample (i.e. uncoated side) was masked with“SCOTCHBLUE PAINTERS TAPE”. The repellent surface of the sample wasentirely submerged (e.g. 30 g) in the (e.g. PPG Envirobase) paint for 10minutes at 21° C. The sample was then removed from the paint, themasking tape removed, and the sample orientated vertically by means abinder clip for 1 minute. The bottom edge of the sample was contactedwith a paper towel to wick away paint that may have pooled along thebottom edge of the material. The weight of each sample was againmeasured and the amount of paint remaining per area was calculated. Thepaint remaining on the coated surface was visually estimated andexpressed as percentage of retained paint coverage.

Unless specified otherwise, the test paint for determining paintrepellency according to the test methods described herein was PPGEnvirobase automobile paint mixed to specification containing 90 weight% ENVIROBASE HIGH PERFORMANCE T409 DEEP BLACK and 10 weight % ENVIROBASEHIGH PERFORMANCE T494 PAINT THINNER, available from PPG Industries,Pittsburgh Pa. or available from 3M, St. Paul, Minn.

Example 100 (EX100)—Preparation of Film with Siloxane Melt Additive

A siloxane melt additive (alkyl dimethicone) was synthesized asdescribed in Example 14 of U.S. Pat. No. 9,187,678, (SMA). The alkyldimethicone was compounded into NA217000 LDPE (Lyondell Basell, Houston,Tex.) at a loading of 15 wt. % using a 25 mm twin screw extruder held at190° C. The alkyl dimethicone was delivered to the extruder as a liquidat 120° C. by means of a heated gear pump and transfer line. Themasterbatch melt was extruded through a stranding die into a chilledwater bath and pelletized at a rate of 13.6 Kg/hour.

These 15 wt. % alkyl dimethicone masterbatch pellets were then admixedwith NA217000 LDPE pellets at a ratio which yielded a pellet mixturecomprising 3 wt. % alkyl dimethicone in LDPE. This 3 wt % alkyldimethicone mixture was extrusion coated sequentially onto both sides of2 mil thick PET film (primed on both sides, 3M Company) using thefollowing procedure. The pellet blend was fed, via a single feed hopper,at a rate of 20 lbs/hr into an extruder and die operating at atemperature of 500° F. The composite extrudate exited the drop dieopening and traveled approximately 10 cm to a nip where the compositewas contacted with the primed PET and solidified through a two roll nipequipped with a rubber and a steel roller. The alkyl dimethicone/LDPElayer contacted a smooth chilled steel roll which was used to acceleratethe solidification of the layers. The line speed was 50 ft/min, yieldingan extruded layer thickness of 1 mil. The final film constructionconsisted of a 2 mil thick PET film sandwiched between 1 mil thicklayers comprising 3 wt. % alkyl dimethicone in LDPE.

The paint repellency of EX100 was also evaluated according to TestMethod 2 as previously described. The results were as follows:

Mass Paint on Percentage of Surface Example Surface (g/cm²) Coated withPaint EX100 0.00074 5%

The paint repellency of EX100 was also evaluated according to TestMethod 6 as previously described using a 4 cm×4 cm sample size. Theresults were as follows:

Mass Paint on Percentage of Surface Example Surface (g/cm²) Coated withPaint EX100 0.0035 15%

Surface Abrasion Test

A sample of sufficient size (e.g., 6 cm by 2 cm) was prepared andmounted on a Taber Abraser (Taber Industries 5750 Linear Abraser). Acrockmeter square (AATC Crockmeter Square from Testfabrics, Inc.) wasattached to the abraser head by means of a rubber band. No additionalweights were placed on top of the abraser head. The cycle speed was setto 15 cycles/min, and each substrate was subjected to 2 abrasion cycles(or in other words the abraser head passed back and forth twice).

Contact angles with a solution containing 10% by weight of2-n-butoxyethanol and 90% by weight deionized water and paint repellencywere tested after being subjected to this surface abrasion.

10% (by wt.) aqueous 2-n-butoxyethanol Contact Angles After AbrasionPaint Repellency CAH After Abrasion Example θ_(adv) θ_(rec) (θ_(adv) −θ_(rec)) Test Method 4 EX100 53 45 8 Pass

The repellency of EX100 after abrasion was also evaluated by measuringthe contact angles with water as previously described. The results wereas follows:

Water Contact Angles After Abrasion CAH Example θ_(adv) θ_(rec) (θ_(adv)− θ_(rec)) EX100 109 99 10

The paint repellency of EX100 after abrasion was also evaluatedaccording to Test Method 2 with the PPG paint as previously described,except 2.2 cm×3.2 cm substrates were used in place of 4 cm×4 cm samples.The results were as follows:

Mass Paint on Fraction of Surface Surface (g/cm²) Coated with PaintExample After Abrasion After Abrasion EX100 0.00040 <5%

The paint repellency of EX100 after abrasion were also evaluatedaccording to Test Method 6 with PPG paint as previously described,except 2.2 cm×3.2 cm substrates were used in place of 4 cm×4 cm samples.The results were as follows:

Mass Paint on Fraction of Surface Example Surface (g/cm²) Coated withPaint EX100 0.0018 10%

Materials

Material Designation Description Obtained from NA217000 NA217000 lowdensity Lyondell Basell, LDPE polyethylene Houston, TX Marflex 1122Marflex 1122 low density Chevron Phillips, The LDPE polyethyleneWoodlands, TX butoxyethanol 2-n-butoxyethanol Alfa Aesar, Ward Hill, MAUHMW Siloxane Dow Corning ® MB50-002 Dow Corning, Midland, ultra highmolecular weight MI siloxane dispersed in low density polyethylene IPAisopropanol BDH Chemicals/VWR, Radnor, PA NMP n-methyl-2-pyrrolidone TCIAmerica, Portland, OR Lexan ™ 1414T Lexan ™ EXL1414T Saudi Arabia Basicpolycarbonate-siloxane Industries Corporation copolymer (SABIC), Riyadh,Saudi Arabia PPS ™ liners thermoformed low density 3M polyethylene (400ml)Preparation of Additional Examples with Siloxane Melt Additive

Two cast web films with an overall film thickness of ˜40 mils—PE101 andPE102—were produced using the SMA/NA217000 masterbatch. Both filmscomprised 3 layers of approximately equal thicknesses (˜13.3 mils perlayer, total thickness about 40 mils). For PE101, all layers wereproduced by mixing pellets of the aforementioned masterbatch withpellets of NA217000 LDPE such that the composition of each layercomprised 97/3 (by wt) NA217000/SMA. The outer (A or air-side) layer wasproduced by extruding the 97/3 LDPE/SMA mixture through a 27 mm twinscrew extruder through a neck tube and gear pump into the top layer ofthe 3 layer feed block and die. This melt train used a progressivetemperature extrusion profile, with peak temperatures of ˜250° C. Themiddle (B) layer was produced by extruding the 97/3 LDPE/SMA mixturethrough a 27 mm twin screw extruder with a progressive temperatureprofile peaking at or around 275-280° C. through a neck tube and gearpump into the middle layer of the feed block and die. The bottom (C orwheel side) layer was produced by extruding the 97/3 LDPE/SMA mixturethrough a 25 mm twin screw extruder through a neck tube and gear pumpinto the bottom layer of the feed block and die. Once again, aprogressive temp profile was used with peak temperatures of 280 to 285°C. The feedblock/die was held at a target temp of 270 to 275° C. whilethe casting wheel was run at about 80-85° C. Film PE102 was made usingessentially identical processing conditions as PE101, except thecomposition varied from layer to layer in this sample. The air-side (A)and middle (B) layers comprised Marflex 1122 LDPE, whilst the wheel side(C) layer comprised a mixture of NA217000/SMA masterbatch and Marflex1122 such that the C layer composition was 85/12/3 (by wt) Marflex1122/NA217000/SMA.

Both of the 40 mil thick film samples were thermoformed into 400 ml PPS™liners, summarized as follows:

SMA Example Loading Sample Description CE1 0 commercial 400 mL PPS ™liner EX101 3 wt. % 3 wt. % SMA in NA217000 LDPE EX102 3 wt. % 3 wt. %SMA in NA217000 LDPE/ in ‘skin’ Marflex 1122 LDPE ‘skin,’ backed byMarflex 1122 LDPE

A polycarbonate-siloxane copolymer coating was prepared by dissolving2.5 wt.-% of the indicated polymer in solvent as described below.

Wt. % Polycarbonate- Solvent Siloxane Polycarbonate-Siloxane Polymer(s)Coating 1 - 80/20 2.5 Lexan ™ 1414T NMP/IPA

To prepare Example EX103, the coating solution was applied to the insidewalls of the spray gun paint container using a pipette as follows: thebottom of a LDPE PPS™ container was first wet with the coating solution,and the solvent was allowed to evaporate under ambient conditions. Thecontainer was then tilted 90° and a pipette was used to coat a strip ofthe interior side wall of the container. Next, the container wasmanually rotated to obtain complete wetting of the entire interiorsidewall by the coating solution. Excess coating solution was drained byflipping the container upside down, and the solvent was allowed toevaporate in an oven at 80° C. for 15 minutes (polyethylene liners).Paint repellency was determined according to Test Method 3 as follows:

Paint containers or spray application system coated withpolycarbonate-siloxane materials.

Coating Identity of Polycarbonate- Example Base Container MaterialSiloxane Polymer(s) EX103 400 mL Coating 1 Lexan ™ 1414T polyethylenelinerThe paint repellency of the aforementioned containers having therepellent interior surfaces and comparative containers was evaluatedaccording to Test Method 3 as previously described. The mass of thecontainers was also measured after 5, 90, and 180 minutes.Paint repellency of sample paint containers as quantified using TestMethod 3.

Mass Mass of Paint Retention Mass Per Empty Following Drainage TimeSurface Area Liner Specified in Row Below (g) Calculation Example (g) 5min 90 min 180 min (at t = 90 min, g/cm²) CE1 5.89 8.72 4.28 3.39 0.015EX101 5.86 3.53 0.84 0.44 0.004 (80% less paint retained*) EX102 5.487.61 1.67 1.05 0.006 (61% less paint retained) EX103 5.83 8.14 1.64 0.540.006 (62% less paint retained) *(4.28 − 0.84)/4.28 × 100%

Preparation of LDPE/Ultra High Molecular Weight (UHMW) Siloxane Film(EX104).

A film comprising 97.5/2.5 (by wt) LDPE/UHMW siloxane was produced byadding 9.5 g LDPE (Chevron Phillips Marflex 1122) and 0.5 g of UHMWsiloxane masterbatch (Dow Corning MB 50-002; 50/50 by wt siloxane/LDPEpellets) into a DSM compounder (DSM Xplore Micro 15 cc Twin ScrewCompounder). The compounder was held constant at 170° C. and the screwspeed was set to 40 rpm/10,000 N. After allowing the melted resin torecirculate and mix in the compounder for 10 minutes, the melt wasextruded through a slotted die and the resultant 28 mm wide, 0.1-0.2 mmthick film was wound onto a 3″ fiber core.

Fluid Contact Angles and Paint Repellency of Various Test Surfaces

Pieces were cut from the sides of a commercially available 400 mL PPS™liner, from the sides of the thermoformed SMA-containing liners (EX101and EX102), from the sides of the polycarbonate-siloxane coated LDPEliners (EX103), and from the roll of LDPE/UHMW Siloxane (EX104). Thesecut pieces of film were used for contact angle testing with water andwith a solution containing 10% by weight of 2-n-butoxyethanol and 90% byweight deionized water instead of deionized water. The measured contactangle data for these samples are provided below, along with thecharacterization data for these samples using Paint Repellency TestMethod 4.

10% (by wt.) aqueous 2-n-butoxyethanol Water Contact Angles ContactAngles CAH CAH Paint Exam- (θ_(adv) − (θ_(adv) − Repellency ple θ_(adv)θ_(rec) θ_(rec)) θ_(adv) θ_(rec) θ_(rec)) Test Method 4 CE1 105 95 10 5121 30 Fail EX101 111 95 16 54 46 8 Pass EX102 111 99 12 55 46 9 PassEX103 107 99 8 54 45 9 Pass EX104 116 87 29 60 40 20 Pass

Paint Repellency was also evaluated according to Test Method 2

Mass Paint on Fraction of Surface Example Surface (g/cm²) Coated withPaint CE1 0.022 ~95% EX101 0.004 ~15% EX102 0.006 ~10% EX103 0.006 ~20%EX104 0.003 ~25%

Paint Repellency was also evaluated according to Test Method 6 aspreviously described using a 4 cm×4 cm sample size.

Mass Paint on Fraction of Surface Example Surface (g/cm²) Coated withPaint CE1 0.022 ~95% EX101 0.004 ~15% EX102 0.006 ~20% EX103 0.007 ~25%EX104 0.013 ~60%

The test surfaces EX1-EX3 and EX5 were subjected to the Surface AbrasionTest. Contact angles with a solution containing 10% by weight of2-n-butoxyethanol and 90% by weight deionized water and paint repellencyas quantified by Test Method 4 were measured after each test substratewas subjected to this surface abrasion.

10% (by wt.) aqueous 2-n-butoxyethanol Contact Angles After AbrasionPaint Repellency CAH Test Method 4 Example θ_(adv) θ_(rec) (θ_(adv) −θ_(rec)) After Abrasion EX101 54 44 10 Pass EX102 53 44 9 Pass EX103 5043 7 Pass EX104 63 38 25 Pass

The repellency after abrasion were also evaluated by measuring thecontact angles with water as previously described. The results were asfollows:

Water Contact Angles After Abrasion CAH Example θ_(adv) θ_(rec) (θ_(adv)− θ_(rec)) EX101 108 92 16 EX102 112 96 16 EX103 106 93 13 EX104 111 8130

Paint Repellency was also evaluated according to Test Method 2, except2.2 cm×3.2 cm sized samples were used in place of 4 cm×4 cm samples.

Mass Paint on Fraction of Surface Surface (g/cm²) Coated with PaintExample After Abrasion After Abrasion EX101 0.003  ~5% EX102 0.003 ~10%EX103 0.002  ~5% EX104 0.005 ~20%Panel Painting Using Base Coats which had Contacted Siloxane-FunctionalMaterials

Two types of experiments were done to ascertain whether “fish-eyeing” isproblematic when waterborne base coats contact the siloxane-functionalsurfaces described herein. The first type of experiment involved pouringa ready-to-spray paint mixture into the repellent containers ofEX101-EX103. The “ready-to-spray” mixture contained 88 wt. % ofENVIROBASE HIGH PERFORMANCE T407 JET BLACK and 12 weight % ENVIROBASEHIGH PERFORMANCE T494 PAINT THINNER, available from PPG Industries.

These repellent containers were used in conjunction withindustry-standard spray application equipment to spray PPG Envirobasepaint. Once this base coat was dry, a coat of clearcoat was applied tothe panel (the clearcoat was obtained from PPG Industries, Inc. as thetrade designation EC530 PERFORMANCE CLEARCLOAT). The paint could beuniformly applied at a sufficient film build. There was no evidence of“fisheyes” or other incompatibility-related coating defects whileapplying the paint and/or by uneven gloss and/or color.

The second type of experiment was completed with the UHMW siloxanematerial. In this experiment, 6.3 g of the MB50-002 resin pelletsobtained from Dow-Corning (siloxane content of 50%) and 50 g theready-to-spray paint mixture were mixed in a commercial 400 mL PPS™liner. The pellets were soaked in the Envirobase at room temperature for7 days, at which point the Envirobase base coat and EC530 clearcoat weresprayed onto an automotive panel as described above. The paint could beuniformly applied at a sufficient film build, and there was no evidenceof “fisheyes” or other incompatibility-related coating defects whileapplying the paint and/or by uneven gloss and/or color.

Some additional test liquids were utilized to evaluated liquidrepellency using Test Method 2. The length of time the sample film washeld vertically to allow the liquid to drain in indicated. The testresults are as follows:

Results for CE1 Results for EX101 (LDPE) (97/3 LDPE/SMA) Average AverageAverage % of Average % of Retained Surface Retained Surface Mass (mg)Covered Mass (mg) Covered Test Liquid (g/cm²) by Fluid (g/cm²) by FluidPoly(propylene glycol), 70.7 75 15.5 5 400 Mw (Polysciences (0.0044)(0.00097) Inc., Warrington, PA) - 30 minutes Butoxyethanol (100%) -(0.0019) 100 (0.00094) 1 0.5 ml applied and a 30 second drain timeSolution of 50 wt. (0.0018 95 (0.000163 5 % butoxyethanol and 50 wt. %water - 0.5 ml applied and a 30 second drain time

1. A component of a spray application system, the component comprising aliquid repellent surface such that the receding contact angle with asolution containing 10% by weight of 2-n-butoxyethanol and 90% by weightdeionized water is at least 35 degrees; wherein the liquid repellentsurface comprises a surface layer comprising a silane or siloxanematerial and liquid repellent surface is not a lubricant impregnatedsurface.
 2. The component of claim 1 wherein the liquid repellentsurface comprises a solid liquid repellent material.
 3. The component ofclaim 1 wherein the siloxane material comprises at least 50 wt.-%polydimethylsiloxane.
 4. The component of claim 1 wherein the siloxanematerial comprises a siloxane backbone and hydrocarbon side chainsaveraging at least 8 carbon atoms and no greater than 50 carbon atoms.5. The component of claim 1 wherein the siloxane material comprisingpolydimethylsiloxane does not comprise vinyl groups or other groups thatform a crosslinked network.
 6. (canceled)
 7. The component of claim 1wherein the siloxane material has a viscosity at 25° C. of 5,000,000 or10,000,000 centistokes.
 8. (canceled)
 9. The component of claim 1wherein the siloxane material is a copolymer comprising less than 50wt.-% polydimethylsiloxane.
 10. The component of claim 9 wherein thesiloxane material is copolymer of polyorganosiloxane and polyolefin orpolycarbonate.
 11. The component of claim 1 wherein the liquid repellentsurface is liquid repellent after 2 abrasion cycles at 15 cycles/minutewith a Taber Linear Abraser.
 12. The component of claim 1 wherein thecomponent is a liquid reservoir, a liquid reservoir liner, a lid for aliquid reservoir or liner, or a combination thereof.
 13. The componentof claim 12 wherein the component comprises a thermoplastic polymericmaterial.
 14. The component of claim 12 wherein the component is aremovable liquid reservoir liner.
 15. (canceled)
 16. The component ofclaim 12 wherein the spray application system further comprises agravity-fed spray gun.
 17. The component of claim 1 wherein the liquidrepellent surface layer repels water-based paint having a volatileorganic solvent of at least 5, 10, 15, 20, or 25 g/liter; wherein thevolatile organic solvent is water-soluble.
 18. (canceled)
 19. Thecomponent of claim 17 wherein the organic solvent comprises one or morealcohol.
 20. (canceled)
 21. The component of claim 17 wherein theorganic solvent comprises 2-butoxyethanol, butoxypropan-2-ol,2-(2-butoxyethoxy)ethanol, and mixtures thereof.
 22. The component ofclaim 1 wherein the liquid repellent surface is liquid repellent suchthat retained paint has a mass no greater than 0.01 g/cm² or a drop ofpaint slides off the liquid repellent surface when oriented vertically.23. (canceled)
 24. The component of claim 1 wherein the liquid repellentsurface has a receding contact angle with water from 90 degrees to 135degrees.
 25. (canceled)
 26. A component of a spray application system,the component comprising a liquid repellent surface such that the massof retained test liquid is no greater than 0.01 g/cm² when the testliquid is selected from 400 Mw polypropylene glycol, butoxythanol, or a50 wt. % aqueous solution of butoxyethanol; wherein the liquid repellentsurface comprises a surface layer comprising a silane or siloxanematerial and the liquid repellent surface is not a lubricant impregnatedsurface.
 27. (canceled)
 28. A spray application system comprising aspray gun, a liquid reservoir that attaches to the spray gun, optionallya liner for the liquid reservoir, a lid for the liquid reservoir and/orliner; wherein at least the liquid reservoir and/or liner comprising aliquid repellent surface layer as described in claim 1.